Novel alkylarylsulfonates



United States Patent O 3,505,395 NOVEL ALKYLARYLSULFONATES Claude H. Trottier, Lincoln, R.I., and Louis Long, Jr.,

Concord, Mass., assignors to the United States of America as represented by the Secretary of the Army N Drawing. Filed Oct. 13, 1966, Ser. No. 587,383 Int. Cl. C07c 143/38; Clld 3/065 US. Cl. 260-505 3 Claims ABSTRACT OF THE DISCLOSURE Novel sulfonyl, sulfinyl, monothia and dithia substituted alkylarylsulfonates useful as water soluble surface active agents.

This invention relates to a novel class of alkylarylsulfonate compounds wherein at least one of the methylene groups of the alkyl chain is replaced by sulfur or an oxide of sulfur.

The novel compounds of this invention have the following formula:

SOI'NIP wherein M is a cation; and X is a member of the group consisting of 0 (CH2) X 2) y a O (CHz),s-(CH2),(JH,

with a being a whole integer from 1 to 8 and b being a whole integer from 0 to 7, with the sum of a and b being 8; with n and m being whole integers from 0 to 8, with the sum of n and m being 8; With x and y being whole integers from 0 to 10, with the sum of x and y being 10.

The novel compounds of this invention are surface active agents, and have excellent detersive properties comparable to n-dodecylbenzenesulfonate. While M in the formula above may be any cation, because these compounds are useful as surfactants, it is preferred that the cation be one which will cause the compound to be readily soluble in water such as members of the class consisting of alkali metals, alkaline earth metals, ammonium, and alkanolamines, e.g. sodium, potassium, magnesium, and mono-, diand tri-ethanolamine.

The preparation of these novel compounds will be described in detail in the examples which follow.

Salts of dithia-substituted alkylbenzenesulfonates having the formula 3,505,395 Patented Apr. 7, 1970 ice Sodium p-(4,6-dithia-n-dodecyl)benzenesulfonate.-To a mixture of 0.14 g. of sodium in 7 ml. of ethanol there was added 10 ml. of dimethylfor'mamide (DMF) and the mixture stirred for 15 minutes. To this mixture there was added under nitrogen 1.0 g. of n-hexylthiomethylmercaptan in 10 ml. of DMF and the mixture stirred for another 15 minutes. A mixture of 1.8 g. of sodium p-(3-bromopropyl)-benzenesulfonate in 30 ml. of DMF was added to the above mixture under nitrogen and allowed to stand for 12 hours. The mixture was cooled, filtered and the filtrate concentrated under vacuum until a precipitate formed. The precipitate in the concentrated filtrate was filtered, and the crude product was recrystallized from ethanol to give 1.0 g.. (44% yield) of sodium p-(4,6-dithia-n-dodecyl) benzenesulfonate.

The structure of this compound is established by elemental analysis and nuclear magnetic resonance (NMR).

Analysis.-Calcd. for C H S O Na (percent): C, 49.98; H, 6.54; S, 25.02. Found (percent): C, 49.94; H, 6.72; S, 25.12.

The nuclear magnetic resonance exhibited an A B pattern for the aromatic protons indicative of a para-substituted phenyl group. The coupling constant was 8 cps. The methylene group between the two sulfur atoms appeared as a singlet. The benzyl group and the methylene groups adjacent to the sulfur appeared as a multiplet. The intensities found were the same as the calculated values.

The tau value intensities and assignments of the NMR signals for this compound are as follows:

Spectra:

Aromatic 2.27, H 2.87 -SCH S 6.2 8

and 7.4 CH 8.55 CH 9.01 Intensities 2:2:2:6:10:3

Salts of sulfinyl substituted alkylbenzenesulfonatcs are formed by reacting a p-(thia-n-dodecyl) benzenesulfomate with an aqueous solution of a sodium metaperiodate. The preparation of p-(thia-n-dodecyl) benzenesulfonates is disclosed in a copending application of Dietrich Lang and Louis Long, Jr., Ser. No. 408,703, filed Nov. 3, 1964 and now U. S. Patent No. 3,344,173, the disclosure of which is incorporated herein by reference.

EXAMPLE II Sodium-p (1 sulfinyl-n-dodecyl)benzenesulfonate.- Sodium p-(l-thia-n-dodecyl) benzenesulfonate is prepared as follows: Sodium (11.5 g., 0.50 mole) was dissolved in 250 ml. of absolute ethanol and 55 g. of thiophenol (0.50 mole) was added. Under external cooling, g. of n-undecyl chloride (0.50 mole) was added and then the reaction mixture was boiled under reflux for 3.5

hrs. The precipitated sodium chloride was filtered, the solvent evaporated, and the residue dissolved in a mixture of petroleum ether and benzene from which the phenyl n-undecyl sulfide crystallized on cooling.

A solution of 20 g. (0.08 mole) of phenyl n-undecyl sulfide in 10 ml. of chloroform was dropped during 1 hr. into 30 ml. (0.45 mole) of chlorosulfonic acid with stirring at 25 C. The reaction mixture was then poured on ice and the organic material extracted with ether. The

ether solution was washed with water, sodium bicarbonate solution, again with water, and dried. Evaporation of the solvent yielded 18 g. (0.05 mole, 65%) of crude p(1- thia-n-dodecyl) benzenesulfonyl chloride. Its infrared spectrum showed the typical absorption bands for the sulfonyl chloride group at 1175 and 1370 cmf In 150 ml. of 60% ethanol, 4.0 g. (0.10 mole) sodium hydroxide and 18 g. (0.05 mole) of the sulfonyl chloride were dissolved, and the mixture was stirred for several hours at room temperature. On cooling the solution in an icebath, sodium p (l thia-n-dodecyl) benzenesulfonate crystallized in colorless leaflets. After three recrystallizations from 50% ethanol, 12 g. (0.03 mole, 65%) was obtained.

To 2.14 g. of sodium metaperiodate (0.0105 mole) in 25 ml. of water was added 3.66 g. (0.01 mole) sodium p-(l-thia-n-dodecyl) benzenesulfonate at to 5 C. The mixture was stirred for 48 hours, filtered and the residue washed with ethanol. The filtrate and washings were concentrated and cooled and the resulting precipitate was collected on a filter. The sodium p-(lsulfinyl-n-dodecyl) benzenesulfonate was obtained in 90% yield. An infrared spectrum of this compound showed the typical absorption band for the sulfoxide (S-O) at 1030 CH1.1. The elemental analysis and NMR spectra for this compound and the sulfinyl compounds obtained in Examples III and IV will be found in Tables I and II respectively.

EXAMPLE III Sodium p-(Z sulfinyl-n-dodecyl) benzensulfonate. Sodium p-(Z-thia-n-dodecyl) benzenesulfonate was prepared as follows: Sodium p-toluenesulfonate (68 g., 0.35 mole) was placed in a 500ml., four-necked flask provided with a mechanical stirrer, a thermometer and a gasinlet and outlet. The flask was immersed in an oil-bath at 120 C., and, with stirring of the dry salt, chlorine was passed in. The internal temperature rose to 145 C. After 75 min. the reactant had gained 11 g. The crude reaction product was twice recrystallized from 90% ethanol. The analysis as well as the nuclear magnetic resonance (NMR) spectrum indicated that this product was a mixture of monoand dichlorinated toluenesulfon-ate. Its NMR spectrum in deuterated water (TMS as an external standard) showed, beside the signals for the phenyl protons around tau 2.4 and the singlet for the benzyl protons at tau 5.37, another singlet at tau 3.04 due to the benzol proton. From the intensities of these signals the proportion of the compounds was calculated to be about 60% alpha-monochloroand 40% alpha-dichlorotoluenesulfonate.

To a solution of 26 g. of this mixture (about 0.10

0 C. This mixture was stirred for 48 hours, filtered and the residue washed with ethanol. The filtrate and washings were concentrated and cooled. Upon cooling a precipitate formed which was then collected on a filter. Sodium p-( 1- sulfinyl-n-dodecyl) benzenesulfonate was obtained in 80% yield. Infrared spectrum showed the typical absorption band for the sulfoxide at 1030 CIR-1.

EXAMPLE IV Sodium p-(N-sulfinyl-n-dodecyl) benzenesulfonate. N is 3 to 11 inclusive. The sodium salts of p-(N-thia-ndodecyl) benzenesulfonate, where N is 3 to 11 were obtained by the following general procedure. The chloroalkyl-benzene (1.0 mole) was added dropwise during 1.5 hrs. to chlorosulfonic acid (10.0 moles) with eflicient stirring, and external cooling by a water-bath at temperatures between 0 and 25 C. The reaction mixture was stirred for another hour and then poured onto ice. The aqueous mixture was extracted with ether, the ether layer was separated from the water layer, and the ether removed by evaporation in vacuum. The residue was purified by distillation under reduced pressure.

The purified chloroalkylbenzenesulfonyl chloride (1.0 mole) was added to a solution of sodium hydroxide (2.0 moles) in water (5.9 ml. of water per gramof sodium hydroxide), and the heterogeneous reaction mixture was stirred vigorously until it became homogeneous. The solution was neutralized with hydrochloric acid and evaporated to dryness. Recrystallization of the residue from ethanol yielded crystalline sodium p-(chloroalkyl) benzenesulfonate.

A mixture of equimolecular quantities of sodium p- (chloroalkyl)-benzenesulfonate, sodium hydroxide and n-alkylmercaptan was boiled under reflux for 3 hrs. On cooling the solution, the desired product crystallized. Recrystallization from water, or aqueous ethanol, afforded pure crystalline sodium p-(N-thia-n-dodecyl)-benzenesulfonate.

Sodium p-(N-thia-n-dodecyl) benzenesulfonate compound (0.01 mole), N being any integer from 3 to 11 inclusive, was added to 0.01 mole of sodium metaperiodate in 25 ml. of water at 0 C. The mixture was stirred for 48 hours, filtered, and the residue washed with ethanol. Filtrate and washings were concentrated. On cooling, a precipitate formed, which was collected on a filter. The infrared spectrum of each of the compounds in this series showed the characteristic sulfoxide band at 1030 cm.-

TABLE I Elemental analysis of sodium p-(Sulfinyl-n-dodeeyl) benzenesulfonates Sodium p-(sulfinyl-n- Carbon, per- Hydrogen, Sulfur, percent mole) and (015 mole) of Sodium hydroxlde 400 dodecyl) benzenesulcent(Ca1c. percent (Cale. (Cale. 16.76) ml. of 40% ethanol and 26 g. (0.15 mole) of n-defonate 53.37) Found 7.11) Found Found canethiol were added, and the reactionm-ixture was boiled bsulfinyl h 53 19 mg m 74 under reflux for 2 hrs. After neutrahzauon with hydro- 55 52. 23 7.13 16. 4s chloric acid, the solution was cooled, and the precipitated 23-52 g-gi g g colorless leaflets of sodium p(2-thia-n-dodecyl)-benzene- 53.18 7:23 15:54 snlfonate were recrystallized three times from 50% gggg ethanol. 53. 7. 12 16. 56 Sodium metaperiodate, 214 g. (0.01 mole), in 25 ml. gig gig 12-23 of water was added to 0.01 mole (3.66 g.) of sodium 11-su1rm 1.- 53.40 6.97 16.61 p-(2-thia-n-dodecyl) benzenesulfonate at a temperature of TABLE II NMR spectra of sodium p-(sulfinyl-n-dodecyl) benzenesultonates Compound Aromatic H CHZS- and PhCHf CH;- CH3 Intensities l-sulfinyl. 2. 10 6. 8S 8. 74 2sulfinyl 2.15 2.50 5.77 6. 98 8.74 3-sulfinyl 2.25 2. 68 6.98 8.74 4-su]finyl 2.25 2.70 7.25 5.74 5-sulfinyl 2.23 2. 73 7.26 8.72 6sulfinyl 2.25 2. 73 7.25 8.51 7sulfinyl 2.25 2.72 7.26 7.33 8.62 8-sulfinyl 2.20 2.75 7.25 8.68 Q-sulfinyL- 2.25 2.73 7.30 7.41 8.79 lO-sulfinyl 2.22 2.76 7.35 s. 72 11-sulfinyl-- 2.22 2.75 7.22 7.44 8.75

A general feature of all spectra of Table II is an A B pattern with two doublets of equal intensity for the phenyl protons. The coupling constants (J =8 cps.) are the same in all cases. The A B pattern found for the phenyl protons is characteristic of substituents in a benzene ring in the para positions. In some cases, the peaks for the benzyl protons and the protons of the methylene groups that are next to the sulfoxide group are not separated but rather consist of a multiplet. The observed intensities are in all cases identical with the calculated values.

The salts of sulfonyl alkylbenzenesulfonates are formed by reacting a p-(thia-n-dodecyl) benzene sulfonate with ozone as illustrated in Example V.

EXAMPLE V Sodium p-(N-sulfonyl-n-dodecyl) benzenesulfonates. N being 1 to 11 inclusive. The eleven isomers of sodium p-(N-sulfonyl-n-dodecyl) benzene sulfonate wherein the sulfonyl group is located in any one of the 1 through 11 position of the alkyl chain are prepared by the following general procedure wherein 0.1 mole of sodium p-(N-thian-dodecyl) benzenesulfonate is added to 250 ml. of methylene chloride and 100 ml. of methanol and the solution (placed in a flask fitted with a fritted cylindrical tube. Ozone gas was passed through the tube for four hours. The solvent was concentrated in vacuo and the precipitate recovered by filtration. The sulfone was recrystallized from ethanol-water to quantitative yield. The infrared spectrum of each of the eleven isomers thus prepared showed the presence of the sulfone bands at 1310 and 1130 MIL-1. The elemental analysis and NMR spectra for the eleven isomers thus prepared are set forth in Tables III and 1V respectively.

TABLE III Elemental analysis of sodium p-(sulfonyl-n-dodecyl) benzenesultonates Hydrogen,

thesized by reacting an n-alkylmercaptan with the salt of a para-substituted haloalkylbenzenesulfonate.

EXAMPLE VI Sodium p-(lmethyl-S-thia-n-undecyl) benezenesulfonate.To 0.01 mole of sodium p-(1-methyl-4-bromopropyl) benzenesulfonate in 150 ml. of ethanol-water was added 0.01 mole of n-hexylmercaptan and 0.02 mole of sodium hydroxide in 50 ml. of water. The reaction mixture was refluxed for four hours, cooled, filtered and the residue recrystallized from ethanol-water to give sodium p-(l methyl 5 thia-n-undecyl) benzenesulfonate. The structure of this compound was established by elemental analysis; NMR and infrared spectra. The tau value, intensities, and assignments of the NMR signals of the compound are as follows:

Aromatic 2.24 H I 2.82 CH 6.34 CH S "I 7.57 CH and CHCH 8.62 CH 8.95 Intensities 2:2:l:4:l5:3

The NMR spectrum shows the A B pattern for the phenylprotons indicative of a para-substituted benzene ring, having a coupling constant (J of 8 cps. The methyl group attached to the methine proton and the methylene groups are not separated and appear as a multiplet. The observed intensities are identical with the calculated values.

Elemental analysis.Calcd. (percent): C, 55.71; H, S, 17.50. Found (percent): C, 55.70; H, 7.40; S,

The synthesis of other isomers in this series can be accomplished by the same procedure as set forth in Example VI.

EXAMPLE VII Sodium p-(1methyl-5-sulfinyl-n-undecyl) benzenesul- S0diu1Ii)pt-)(sull0nyll1ncarp peg m- 6 Stlfau1Ldper3ent f0nate.-To 0.01 mole of sodium metaperiodate in 25 ml.

dodecy enzenes cen ac ac C c .1.10)

1.0mm 5123) Found Found Found of water was added 0.01 mole of SOdlllIIl p-(l-methyl-S- thia-n-undecyl) benzenesulfonate (Example VI) at 0 gg lgggl g; Th mix ure w s stirred for 48 hours, filtered and the 3 u%f ny% g 2.7; 15,90 residue washed with ethanol. The filtrate and washings 2 :2 were concentrated, cooled and the precipitate collected g-suullgonyl 1% o give the sulfoxrde. The structure of th compound was j ggg 51:30 15:87 elucidated by elemental analysis, infrared spectra and as 29 12- c 1H mfongl 682 NW5 0 Elemental analysis. alcd. (percent): C, 53.37; H, 5 7.11; S, 16.76. Found (percent): C, 53.32; H, 7.11; S,

TABLE W 16.70.

N MR spectra of sodium p-(sulfonyl-nd0decyl) benzeuesulionates Cornpound Aromatic H CH2S and PhCHr CH3- CH Inte itie l-sulfonyL- 2.05 6.78 8.72 9.12 2:212:1813

2-sulfouyl- 2.17 2.57 5.67 6.95 8.70 9.12 2=2=4=2=14=3 3-sulionyL- 2.27 2.72 6.85 6.97 8.70 9.12 2=2;4=2;14=3

4-sulfonyl 2.25 2.75 5.97 7.25 8.72 9.12 2:2:4'2:l4=:3

5-sulionyl 2.27 2.73 6.94 7.37 8.72 9.12 212$. =14=3 fi-sulfonyL- 2.27 2.73 6.97 7.40 8.60 9.13 221421413 7-sulionyl 2.35 2.72 7.05 7.42 8.62 9.15 221421413 8-sulionyL- 2.27 2.75 6.95 7.38 8.65 9.12 212421413 9-sulionyl. 2.27 2.72 7.02 7.47 8.72 9.01 21241211413 10-su1ionyL 2.25 2.74. 7.00 7.45 8.74 8.88 2214:2143

ll-sulfonyl- 2.24 2.73 7.05 7.88 8.73 7.05 2:2:2:2:l6:3

The A B pattern characteristic of a para-substituted benzene ring is evident in Table IV. The coupling constants (J =8 cps.) is the same for the aromatic phenyl protons. The peaks for the benzyl protons and methylene group next to the sulfone are separated in all cases except for the l-substituted sulfone. The observed intensities are in all cases identical with the calculated values.

The salts of isomers of p-(l-methyl-N-thia-n-undecyl) benzenesulfonate where N is 3 to 10 inclusive can be syn- The tau value, intensities, and assignments of the NMR signals of the compound are as follows:

The NMR spectrum shows an A B pattern for the phenyl protons indicative of a para-substituted benzene ring, with a coupling constant (J of 8 cps. The methine proton and methyl group adjacent to the sulfoxide group appears as a multiplet. The intensities found are as calculated.

The infrared spectrum shows an absorption band at 1030 cm? indicative of the sulfoxide group.

The isomers of p-(1-methyl-N-sulfonyl-n-undecyl) benzenesulfonates where N is 2-10 inclusive, are formed by reacting the appropriate p-(l-methyl-N-thia-n-undecyl) benzenesulfonate with ozone. The following example is illustrative of this synthesis.

EXAMPLE VIII Sodium p-(1-methyl-S-sulfonyl-n-undecyl) benzenesulfonate.To 0.1 mole of sodium p-(1-methyl-5-thia-nundecyl) benzenesulfonate (Example VI) was added to 250 ml. of methylene chloride and 100 ml. methanol. The solution was placed in a flask equipped with a fritted cylindrical tube and ozone gas passed through the tube for 4 hours. The solvent was evaporated and the precipitate collected and recrystallized from ethanol-Water to give sodium p-(1-methyl-S-sulfonyl-n-undecyl) benzenesulfonate.

Elemental analysis.Calcd. (percent): C, 51.23; H, 6.83; S, 16.01. Found (percent): C, 51.00; H, 6.77; S, 16.01.

The tau value, intensity and assignment of the NMR signals are as follows:

Aromatic 2.22

--CH--+CH SO 7.10 -SO CH +(CH 8.72 --CH 9.15 Intensities 2:225:15 :3

The NMR spectrum shows an A B pattern for the aromatic protons indicative of a para-substituted benzene ring with a coupling constant (J of 8 cps. The methine proton and the methylene group adjacent to the sulfone appear 'as a multiplet. The intensities found are as calculated.

The infrared spectrum shows absorption bands at 1310 and 1130 cm.- indicative of the sulfone group.

The nuclear magnetic resonance spectra were recorded on a Varian 60 Mc spectrometer at 60 C. The samples to be tested were dissolved in deuterated water with sodium 2,2-dimethyl-2-silapentane-S-sulfonate (DDS) as internal standard (tau=10.00 for the trimethylsilyl protons). The infrared spectra were recorded on a Beckman 1R9 spectrophotometer using KBr pellets.

Certain of the novel compounds of this invention possess a further advantageous property in that they are unexpectedly, highly biodegradable. Biodegradability in this context refers to the ability of a surfactant to be broken down in waste water by biological agents naturally present therein, for example, microbes. Since surfactants are undesirable contaminants when found in Water supplies and adversely affect sewage and waste treatment processes because of their foaming and suspending action, it is of great importance that these compounds be rapidly and completely broken down.

Table V indicates the percent of surfactant biodegraded at different time intervals employing the River Die-Away Test wherein a mg. sample of the surfactant is dissolved in' /z liter of river water and allowed to incubate at C. The contents were mixed for one minute prior to sample withdrawal and the samples analyzed by the standard methylene blue method described by J. C. Vaughn in the I. Am. Water Works Assoc., 50, No. 10, 1343 (1958). The standard employed herein is the standand soft detergent of the Soap and Detergent Association and is a mixture of isomers of dodecyl benzenesulfonate (LAS) with approximately of the isomers having the phenyl group attached to the 2 position d the alkyl chain and the remaining 20% consisting of other isomers.

Table VI indicates the percent of surfactant biodegraded at different time intervals using the Shake Flask Culture Procedure of the Soap and Detergent Association. A mixed microbial culture originating from activated sludge of a waste treatment plant was used for all shake flask degradation studies. The surfactant (20 g. per 1.) was placed in a shake flask and sterilized in an autoclave at 20 p.s.i.g. for twenty minutes. After sterilization and cooling, the flask is innoculated with 10 ml. per liter of an adapted 72 hour mixed microbial culture. The innoculated surfactant solution was then incubated on a reciprocated shaker at 25 C. The standard employed is the same as that used in Table V.

TABLE V Percent Biodegradation of the Surfactant in Passaic River Water Sample 6 days 12 days (1) Standard (LAS) 15 75 (2) Sodium p(4,6-dithian-dodecyl) benzenesultonate 72 86 (3) Sodium para-(1-sulfinyln-dodecyl) benzenesulfonate 97 (4) Sodium para-(2-sulfinyl-n lodecyl) beuzeuesull'ouate 72 86 (5) Sodium para-(3-sulfinyl n l0decyl) beuzencsulfonate 38 (6) Sodium para-(5-sulfinyl-n-dodeeyl) benzenesulfonate 56 98 (7) Sodium para-(ll-sulfinyl-n-dodecyl) benz euesulfonate 48 62 (8) Sodium para-(l-sulfon benzencsulfonate 90 96 (9) Sodium para-(2sulIOn Ln-dodecyl) benzenesulfonate 54 32 (10) Sodium para-(S-sulfonyl-n-dodecyl) benzencsulfonate 86 98 (11) Sodium para-(4-sulfonate-n-dodecyl) benzen esulfonatc 98 99 (12) Sodium para-(5-sultonyl-n-dodecy1) beuzenesulfonate 7 4 92 (13) Sodium para-(ll-sulfonyl-n-dodecyl) enzenesulfonate 30 58 TABLE VI Percent Biodcgradation of the- Surfactant by the Shake Flask Culture Procedure of the Soap and Detergent Association Sample 4 days 6 days 8 days 1) Standard (LAS). 82 96 98. 3 (2) Sodium p(4,6dith bcnzcncsulfonate 94 98 99. 6 (3) Sodium paradl-sulfinyl-mdodecyl) benzcnesulfonate 98 100 (4) Sodium para-(-sulfinyl-n-dodecyl) benzenesulfonate 96 98 99. 6 (5) Sodium para-(S-sulfinyl-n-dodecyl) bcnzenesulfonate 86 98 99. 9 (6) Sodium para-(4-sultiny benzenesullonate 90 98 99. 6 (7) Sodium para-(5-sulfinyLn-d0decyl) benzenesulfonate 98 99 100 (8) Sodium para-(ll-sulfinyl-n-dodecyl) benzenesultonate 96 99 100 (9) Sodium para-(l-sult'onyl-n-dodecyl) benz enesulr'onate 97 99 100 (10) Sodium para-(2sulf0nyl-n-dodecyl) bemenesullonate 92 96 98 (11) Sodium para-(3 sulfonyl-n-dodecyl) benzenesulfonat-c 96 97 97. 9 (12) Sodium para-( l-sulfonyl-n-dodecyl) benzenesulfonate 97 99 100 (13) Sodium para-(5-sulfonyl-n-dcdecyl) benzencsulfonate 99 99 100 We claim: 1. A compound of the formula:

(CH2)a-S-OH2-S-( CH2) bCHa SO2 M+ wherein M is a cation selected from the group consisting of alkali metals, alkaline earth metals, ammonium and alkanolamines and wherein a is a whole integer from 1 to 8 and b is a whole integer from 0 to 7 with the sum of a and b being 8.

2. A compound according to claim 1 wherein a is 3 and b 5.

3. A compound according to claim 2 wherein M is sodium.

References Cited UNITED STATES PATENTS Schmerling, et al. 260663 Mock 260505 Schultz et a1.

Richter.

Collins et al.

Penzing.

10 3,275,667 9/1966 Bohunek. 3,344,173 9/1967 Long etal 260-505 OTHER REFERENCES 5 Boundy et a1. Styrene, Its Polymers and Derivatives,

LEON ZITVER, Primary Examiner I. E. EVAN S, Assistant Examiner 10 U.S. Cl. X.R. 

